EP0170414B1 - Verfahren zur Behandlung von Metalloberflächen - Google Patents

Verfahren zur Behandlung von Metalloberflächen Download PDF

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Publication number
EP0170414B1
EP0170414B1 EP85304636A EP85304636A EP0170414B1 EP 0170414 B1 EP0170414 B1 EP 0170414B1 EP 85304636 A EP85304636 A EP 85304636A EP 85304636 A EP85304636 A EP 85304636A EP 0170414 B1 EP0170414 B1 EP 0170414B1
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EP
European Patent Office
Prior art keywords
copper
amino
phenanthroline
hydroxy
aminopyrimidine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP85304636A
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English (en)
French (fr)
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EP0170414A2 (de
EP0170414A3 (en
Inventor
Akishi Nakaso
Youichi Kaneko
Toshiro Okamura
Kiyoshi Yamanoi
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Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
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Filing date
Publication date
Priority claimed from JP59135562A external-priority patent/JPS6115981A/ja
Priority claimed from JP59135561A external-priority patent/JPS6115980A/ja
Priority claimed from JP60015807A external-priority patent/JPS61173932A/ja
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of EP0170414A2 publication Critical patent/EP0170414A2/de
Publication of EP0170414A3 publication Critical patent/EP0170414A3/en
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Publication of EP0170414B1 publication Critical patent/EP0170414B1/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/072—Electroless plating, e.g. finish plating or initial plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/901—Printed circuit

Definitions

  • This invention relates to a process for treating surfaces of copper conductors of wiring boards for inner layers which are bonded via prepregs in the production of multilayer printed wiring boards.
  • Multilayer printed wiring boards are usually produced by the following processes:
  • Multilayer printed wiring boards produced by process (1) have insufficient adhesive strength between the inner layer copper conductors and the resin layers obtained by curing the prepregs. Further, when mounting various electronic devices on the thus-produced multilayer printed wiring board with solder, peeling occurs between the inner layer copper conductors and the resin layer obtained by curing the prepregs; sometimes blisters derived from the peeling can be identified by the naked eye from outside.
  • the roughened surface sometimes becomes scratched during the steps prior to formation of the printed wiring on the copper clad laminates. In such a case, the scratched portion has lower adhesive strength. Further, since the roughened surface of a copper foil is used, the pattern definition of the printing etching resist, or the pattern definition of the etching resist used in a UV photographic printing method for forming printed wiring patterns, is poor.
  • the copper oxide film is dissolved by the sensitizing solution used when providing a plating catalyst on through-hole surfaces for forming electroless copper plated films thereon (the sensitizing solution being an acidic solution of pH 4 or less) or by an acidic solution used when removing smears adhered to cut surfaces of inner layer copper conductors after drilling through-holes and the acidic solution permeates between inner layer copper conductor surfaces and resin layers to bring about the pink-ring phenomenon and lower both the adhesiveness between the inner layer copper conductor surface and the resin layer obtained by curing the prepreg and the insulation resistance between conductors.
  • the sensitizing solution being an acidic solution of pH 4 or less
  • an acidic solution used when removing smears adhered to cut surfaces of inner layer copper conductors after drilling through-holes and the acidic solution permeates between inner layer copper conductor surfaces and resin layers to bring about the pink-ring phenomenon and lower both the adhesiveness between the inner layer copper conductor surface and the resin layer obtained by curing the prepreg and the insulation resistance
  • USA-3793038 describes electroless plating onto catalysed surfaces of plastic articles in which various organo-nitrogen compounds are used to stabilise the plating solution.
  • This invention provides a process comprising treating a copper conductor surface with a liquid composition comprising
  • the liquid composition (hereafter "treating solution A”) comprises (I) copper ions, a complexing agent for copper ions, a reducing agent for copper ions, a pH adjusting agent, water, and (II) a nitrogen-containing organic compound.
  • copper ions there can be used those obtained from a copper ion source such as copper sulphate, copper nitrate and cupric chloride, and other conventional copper salts.
  • the complexing agent for copper ions there can be used compounds which form complexes with the above-mentioned copper ions and make the complexes soluble in an aqueous alkaline solution.
  • the complexing agents are ethylenediaminetetraacetic acid (EDTA) or sodium salts (mono-, di, tri- or tetrasodium salts) thereof; N,N,N',N'-tetrakis(2-hydroxy-propyl)-ethylenediamine; nitrilotriacetic acid and its alkali salts; gluconic acid; gluconates; triethanolamine and tartaric acid.
  • formaldehyde and formaldehyde precursors or derivatives such as paraformaldehyde and hypophosphites.
  • the pH adjusting agent for adjusting the pH of the treating solution A there can be used for instance sodium hydroxide or potassium hydroxide.
  • the use of deionized water is preferable.
  • component (I) is as follows:
  • a particular example of the component (I) is as follows:
  • Component (II) is usually used in an amount of 0.1 mg/liter or more. Since the nitrogen-containing organic compounds mentioned above are relatively expensive, the addition of too large an amount is not preferable from the viewpoint of production cost. It is preferable to use in the range of 1 to 500 mg/liter. These compounds of the component (II) are available commercially from for instance Dojindo-Laboratories Co., Ltd., Tokyo Kasei Kogyo Co., Ltd and Aldrich Chemical Co. in U.S.A.
  • Treating solution A is fundamentally an electroless copper deposition bath used for forming conductors on insulating substrates in the production of printed wiring boards.
  • the electroless copper deposition bath conventionally used is so composed as to form an electroless copper deposition having a metallic copper color and metallic copper gloss on the insulating substrates by adding various additives to the component (I).
  • the component (II) is added to the component (I) so as to form an electroless copper deposition having a color and gloss other than those of metallic copper obtained by the conventionally used electroless copper deposition bath on a surface of metal such as copper.
  • an electroless copper deposition layer having minute particles, needles, cylinders, or a mixture thereof in the layer as deposited surface morphology.
  • Such an electroless copper deposition layer has a dark color such as dark brown, grayish brown, bluish violet, bluish black or brownish black with no gloss.
  • Such a color has an average light absorption rate of 0.5 or more, preferably 0.7 or more, using a light of 300 to 800 nm and converted to values so as to meet the wavelength intensity distribution of sunlight.
  • the temperature of the treating solution A depends mainly on the pH and the concentration of reducing agent in treating solution A.
  • the pH or the reducing agent concentration is high, treatment is possible even at low temperatures. Therefore, it is possible to select the temperature from room temperature to about 90°C depending on the composition of the treating solution A.
  • the treatment time is related to the deposition rate of the treating solution A. Since a shorter treating time is preferable, the immersion time in the treating solution A is usually 1 to 60 minutes.
  • the thickness of the plated film is preferably 1 to 5 ⁇ m. But even if the thickness is over 5 ⁇ m, this is no obstacle to improvement in adhesiveness.
  • treating solution B After the treatment of the metal surface with the treating solution A, the treatment with at least one of ammonia water, an aqueous solution containing a reducing agent and an acid solution (hereinafter referred to as “treating solution B”) can give more desirable results.
  • the aqueous solution containing a reducing agent can be prepared by using formaldehyde, paraformaldehyde, hypophosphorous acid or a salt thereof, as a reducing agent.
  • formaldehyde or paraformaldehyde it is preferable to make the aqueous solution alkaline in the pH range of 9.0 to 13.5 in order to provide reducing properties.
  • a complexing agent for copper ions it is possible to add to the reducing aqueous solution.
  • an electroless copper deposition solution containing a copper salt, hydroxyl ions, a complexing agent for copper ions, and formaldehyde but avoid an electroless copper deposition reaction by having too low a concentration of copper salts.
  • the concentration of for instance the reducing agent, the temperature of the solution B and the treatment time can be selected properly so as to achieve the maximum adhesive strength between the treated surface and the resin so long as the glossless and dark colored surface obtained by the treatment with treating solution A is retained.
  • acid solution there can be used an aqueous solution of hydrochloric acid, sulfuric acid or ammonium persulfate.
  • concentration, the temperature and the treatment time of the acid solution can be selected properly so as to achieve the maximum adhesive strength between the treated surface and the resin so long as the glossless and dark colored surface obtained by the treatment with treating solution A is retained.
  • the treatment with treating solution A or B can be conducted by conventional processes such as dipping or spraying.
  • the copper conductors to be treated by this invention can be conductors obtained by either etching the copper foil of copper clad laminates, electroless copper plating of a combination of electroless and electro-plating of copper.
  • the surface of the metal can be pre-treated with an aqueous solution of at least one compound selected from hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid, acetic acid, copper compounds such as cupric chloride and copper sulphate, iron compounds such as ferric chloride and ferric sulfate, alkali metal chlorides or ammonium persulfate, to "roughen” the surface. It is also possible to employ mechanical methods such as liquid honing and abrasion, in place of a chemical "roughening" method.
  • This invention was explained in relation to the treatment of copper conductors to increase the adhesion of wiring patterns on inner layer printed wiring boards, but the treating solution A or A and B used in this invention can also be used for surface treatment of the copper of copper clad laminates to increase the adhesive strength between the copper and a resist which is formed on the copper or surface. It can also be used as a surface treatment of copper conductors to increase the adhesion between the copper conductor surface and a solder resist. That is, when treatment according to this invention is conducted after the formation of copper conductors by an etching method or an additive method, and an insulating resin, e.g.
  • a resist ink or an adhesive is coated or adhered by a screen printing method, a curtain coating method or a hot roll laminating method followed by formation of copper conductors, the adhesive strength between the copper conductor surface and the above-mentioned material can be improved remarkably.
  • a multilayer printed wiring board can be produced without using a pressing step, when conductors are formed on the outer layers of above-mentioned material according to a conventional method.
  • This invention can also be applied to the treatment of the surface of a copper foil to be contacted with a prepreg in the production of copper clad laminates by bonding a laminate of the copper foil and the prepreg, and the treatment of the surface of a copper foil to be contacted with a flexible film in the production of substrates for flexible wiring boards by bonding the copper foil and the flexible film.
  • the adhesive strength between a resin material, such as a prepreg, and copper is improved, the line definition of the inner layer conductors in multilayer printed wiring boards is excellent, and thus there can be obtained printed wiring boards for inner layers having excellent adhesive strength and shelf life.
  • a copper clad laminate wherein an epoxy resin was used which had previously been subjected to a roughening treatment with ammonium persulphate aqueous solution. Then, it was immersed in a treating solution obtained by adding 3 mg/liter of 4,7-dimethyl-1,10-phenanthroline to a fundamental bath composition (A1) at 70 ⁇ 2°C for 20 minutes.
  • the tape test was carried out to examine the adhesive strength of the treated surface.
  • a pressure-sensitive adhesive tape 10 mm wide and with an adhesive on one side (manufactured by Nitto Electric Industrial Co., Ltd.) was attached to the treated surface and stuck tightly until the tape become transparent. Then, the tape was peeled off gradually and the amount of the adhesive remaining on the treated surface was evaluated. The larger the amount of adhesive remaining, the higher the adhesive strength.
  • the adhesive strength was evaluated as follows: X no adhesive was retained; ⁇ the adhesive was retained slightly; o the adhesive was retained on about half of the surface; and o the adhesive was retained on the whole surface.
  • the shelf life test was conducted to examine the period of usable time for bonding with lamination without lowering the adhesive strength. After being allowed to stand at room temperature at ambient moisture for 7 days, the above-mentioned tape test was conducted on the treated surface and evaluated in the same manner as mentioned above.
  • Example 1 The process of Example 1 was repeated except using 100 3mg/liter of 1,10-phenanthroline in place of mg/liter of 4,7-dimethyl-1,10-phenanthroline and making the immersion time 30 minutes in place of 10 minutes.
  • the color of the treated copper surface and the results of the tape test and the shelf life test are listed in Table 1.
  • Example 1 The process of Example 1 was repeated except using 10 mg/liter of ⁇ , ⁇ '-dipyridyl in place of 3 mg/liter of 4.7-dimethyl-1,10-phenanthroline.
  • the color of the treated copper surface and the results of the tape test and the shelf life test are listed in Table 1.
  • Example 1 The process of Example 1 was repeated except using 20 mg/liter of 2,4,6-tris(2-pyridyl)-s-triazine in place of 3 mg/liter of 4,7-dimethyl-1,10-phenanthroline and making the immersion time 5 minutes in place of 10 minutes.
  • the color of the treated copper surface and the results of the tape test and the shelf life test are listed in Table 1.
  • Example 1 The process of Example 1 was repeated except using 10 mg/liter of 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine in place of 3 mg/liter of 4,7-dimethyl-1,10-phenanthroline and making the immersion time 30 minutes in place of 10 minutes.
  • a copper clad epoxy resin laminate was subjected to a roughening treatment with aqueous ammonium persulphate solution.
  • Inner layer circuits were formed on a copper clad laminate (two-sided board) wherein an epoxy resin was used to give a printed circuit board, which was treated as follows:
  • the printed circuit board was subjected to degreasing, roughening with aqueous ammonium persulphate solution, rinsing with water, immersion in a treating solution obtained by adding 10 mg/liter of 4,7-dimethyl-1,10-phenanthroline to the fundamental bath composition (A1) as used in Example 1 at 70°C for 10 minutes, rinsing with water, and drying at 100°C for 30 minutes.
  • the resulting printed circuit board was subjected to pressing with heating with prepregs 3 and copper foils 4 as shown in the attached drawing (pressure 60 kg/cm2, temperature 170°C, time 120 minutes) to give a multilayer printed circuit board.
  • numeral 1 denotes an inner layer circuit substrate and numeral 2 a circuit copper foil formed on the inner layer circuit substrate.
  • Inner layer circuits were formed on a copper clad laminate (two-sided board) wherein an epoxy resin was used to give a printed circuit board, which was treated as follows.
  • the printed circuit board was subjected to degreasing, roughening with aqueous ammonium persulphate solution, rinsing with water, and drying at 100°C for 30 minutes. Using the thus treated printed circuit board a multilayer printed circuit board was produced in the same manner as described in Example 6.
  • Inner layer circuits were formed on a copper clad laminate (two-sided board) wherein an epoxy resin was used to give a printed circuit board, which was treated as follows.
  • the printed circuit board was subjected to degreasing, roughening, washing with water, immersion in aqueous solution (sodium hydroxide 0.5%, trisodium phosphate 1% and sodium chlorite 3%) at 70°C for 1 minute, rinsing with water, and drying at 100°C for 30 minutes.
  • aqueous solution sodium hydroxide 0.5%, trisodium phosphate 1% and sodium chlorite 36%
  • Inner layer circuits were formed on a copper clad laminate (two-sided board) having both-side roughened copper foil wherein an epoxy resin was used to give a printed circuit board.
  • a multi-layer printed circuit board was produced in the same manner as described in Example 6.
  • Copper clad laminates for inner layers previously provided with inner layer circuits were subjected to a roughening treatment with aqueous ammonium persulphate solution, followed by a treatment with the following treating solution (A2) for 15 minutes under the following conditions: Subsequently, the treated inner layer copper clad laminates were treated with a treating solution B and treating conditions as listed in Table 3.
  • the resulting inner layer copper clad laminates were subjected to pressing with heating with prepregs 3 and copper foils 4 as shown in the attached drawing (pressure 60 kg/cm2, temperature 170°C, time 120 minutes) to give multilayer printed circuit boards.
  • Adhesive strength JIS-C 6481 (see footnote of Table 2).
  • Resistance to electroless copper deposition bath A sample of 130 x 30 mm was cut off and surface copper foils thereon were removed. After drilling 36 holes each with a diameter of 1mm, the resulting sample was dipped in the following electroless copper deposition bath. The time required for making the electroless copper deposition bath penetrate into inner layer surfaces was evaluated as follows:
  • a copper clad laminate for inner layers previously provided with inner layer circuits was subjected to a roughening treatment with aqueous ammonium persulphate solution, following by immersion in an aqueous solution containing 0.5% of NaOH, 1% of trisodium phosphate and 3% of sodium chlorite at 70°C for 1 minute.
  • the thus treated copper clad laminate was subjected to pressing with heating in the same manner as described in Examples 7-11 to give a multilayer printed circuit board.
  • a copper clad laminate for inner layers treated with aqueous ammonium persulphate solution and an aqueous solution containing NaOh, trisodium phosphate and sodium chlorite in the same manner as described in Comparative Example 5 was subjected to the same treatment with the treating solution B as described in Example 7. Then, the thus treated copper clad laminate was subjected to pressing with heating in the same manner as described in Examples 7-11 to give a multilayer printed circuit board.
  • Examples 7-11 The process of Examples 7-11 was repeated except that the treatment with a treating solution B was omitted.
  • a multilayer printed circuit board was prepared in the same manner as described in Examples 7-11.
  • Examples 7 - 11 are remarkably improved in adhesive strength, resistance to HCl aqueous solution, and resistance to electroless copper deposition bath compared with Reference Example 1 wherein no treatment with the treating solution B is conducted.
  • Comparative Example 6 the resistance to aqueous HCl solution and the resistance to electroless copper deposition bath are good, but peeling occurs at the adhered surface depending on soldering temperature when parts are mounted on the multilayer printed circuit board with solder due to low inner layer peeling strength.
  • Copper clad laminates wherein an epoxy resin was used were subjected to a roughening treatment with aqueous ammonium persulphate solution, followed by immersion in a treating solution obtained by adding 10 mg/liter of benzoguanamine, 8-azaguanine, xanthopterin, 2-aminopyrimidine-hydrochloride, 2-aminopyrimidine, 6-hydroxy-2,4,5-triaminopyrimidine-sulphate or nitroguanidine to a fundamental bath composition (A3) at 70 + 2°C for 5 minutes.
  • a fundamental bath composition A3
  • Inner layer circuits were formed on copper clad laminates (two-sided boards) wherein an epoxy resin was used to give printed wiring boards, which were treated as follows:
  • the printed wiring boards were subjected to degreasing, roughening with aqueous ammonium persulphate solution, rinsing with water, immersion in a treating solution obtained by adding 15 mg/liter of xanthopterin, 2-aminopyrimidine-hydrochloride or nitroguanidine to the fundamental bath composition (A3) used in Example 12 at 70°C for 5 minutes, rinsing with water, and drying at 100°C for 30 minutes.
  • the resulting printed circuit board was subjected to pressing with heating in the same manner as described in Example 6 to give multilayer printed wiring boards. Properties of the multilayer printed wiring boards were tested and listed in Table 6.
  • Example 13 The process of Example 13 was repeated except that treatment with a treating solution B (1% aqueous HCl solution) at 20-25°C for 30 seconds was inserted after the treatment with the modified fundamental bath composition (A3). Properties of the produced multilayer printed wiring boards were tested and are listed in Table 6.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (8)

  1. Verfahren zur Behandlung einer Kupferleiter-Oberfläche, dadurch gekennzeichnet, daß mit einer flüssigen Zusammensetzung, die
    (I) Kupferionen, ein Komplexierungsmittel für Kupferionen, ein Reduktionsmittel für Kupferionen, ein Mittel zur Einstellung des pH-Wertes, Wasser und
    (II) mindestens eine Stickstoff enthaltende organische Verbindung, ausgewählt unter 2,4,6-Tris-(2-pyridyl)-s-triazin, α,α',α"-Tripyridyl, 1,10-Phenanthrolin, 4,7-Diphenyl-1,10-phenanthrolin, 4,7-Dimethyl-1,10-phenanthrolin, 4,7-Diphenyl-1,10-phenanthrolin-disulfonsäure-dinatriumsalz, 3-(2-Pyridyl)-5,6-diphenyl-1,2,4-triazin, α,α'-Dipyridyl, Phthalocyaningrün, 2,4-Dimethylimidazolin, 8-Azaguanin, Xanthopterin, 5-Aminoindazol, 2-Aminopyrimidin-hydrochlorid, 2-Aminopyrimidin-hydrobromid, Benzoguanamin, Acriflavinhydrochlorid, 5-Amino-1H-tetrazol, 6-Amino-2-phenyl-4-chinolinol, 2-Amino-6,8-dihydroxypurin, 2-Aminopyrimidin, 6-Hydroxy-2,4,5-triaminopyrimidinsulfat, 2,4-Diamino-6-hydroxypyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin, 4,6-Dihydroxypyrimidin, Nitroguanidin, 1-Hydroxy-1H-benzotriazol-monohydrat, 2-Hydroxybenzimidazol und 2-Amino-3-hydroxypyridin, enthält, stromfrei eine Kupferabscheidungsschicht mit einer durchschnittlichen Lichtabsorptionsrate von 0,5 oder mehr unter Verwendung eines Lichts von 300 bis 800 nm und umgewandelt auf Werte, so daß die Wellenlängen-Intensitätsverteilung von Sonnenlicht erfüllt wird, gebildet wird und ein Harz mit der stromfrei abgeschiedenen Kupferschicht verbunden wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die stromfrei abgeschiedene Kupferschicht eine durchschnittliche Absorptionsrate von 0,7 oder darüber besitzt.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die flüssige Zusammensetzung von 1 bis 500 mg/l der Stickstoff enthaltenden organischen Verbindung enthält.
  4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß zusätzlich die stromfrei abgeschiedene Kupferschicht mit mindestens einer Lösung aus der Gruppe Ammoniak-Wasser, einer wäßrigen Lösung, die ein Reduktionsmittel enthält, und einer Säure-Lösung vor dem Verbinden des Harzes mit der Schicht behandelt wird.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß weitere Harzschichten mit dem Metall, dessen Oberfläche behandelt wurde, verbunden werden, so daß ein Laminat aus einer oder mehreren Metallschichten und mehr als einer Harzschicht erhalten wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die flüssige Zusammensetzung mindestens eine Stickstoff enthaltende Verbindung, ausgewählt aus der Gruppe Xanthopterin, 2-Aminopyrimidin-hydrochlorid, 2-Aminopyrimidin-hydrobromid, 6-Hydroxy-2,4,5-triaminopyrimidinsulfat, 2,4-Diamino-6-hydroxypyrimidin und Nitroguanidin, enthält.
  7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die flüssige Zusammensetzung mindestens eine Stickstoff enthaltende heterocyclische Verbindung, ausgewählt unter 2,4,6-Tris-(2-pyridyl)-s-triazin, α,α',α"-Tripyridyl, 1,10-Phenanthrolin, 4,7-Diphenyl-1,10-phenanthrolin, 4,7-Dimethyl-1,10-phenanthrolin, 4,7-Diphenyl-1,10-phenanthrolin-disulfonsäure-dinatriumsalz, 3-(2-Pyridyl)-5,6-diphenyl-1,2,4-triazon, α,α'-Dipyridyl, Phthalocyaningrün und 2,4-Dimethylimidazol, enthält.
  8. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die flüssige Zusammensetzung mindestens eine organische Verbindung, ausgewählt unter 8-Azaguanin, Xanthopterin, 5-Aminoindazol, 2-Aminopyrimidinhydrochlorid, 2-Aminopyrimidin-hydrobromid, Benzoguanamin, Acriflavinhydrochlorid, 5-Amino-1H-tetrazol, 6-Amino-2-phenyl-4-chinolinol, 2-Amino-6,8-dihydroxypurin, 2-Aminopyrimidin, 6-Hydroxy-2,4,5-triaminopyrimidinsulfat, 2,4-Diamino-6-hydroxypyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin, 4,6-Dihydroxypyrimidin, Nitroguanidin, 1-Hydroxy-1H-benzotriazol-monohydrat, 2-Hydroxybenzimidazol und 2-Amino-3-hydroxypyridin, enthält.
EP85304636A 1984-06-29 1985-06-28 Verfahren zur Behandlung von Metalloberflächen Expired - Lifetime EP0170414B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP59135562A JPS6115981A (ja) 1984-06-29 1984-06-29 銅の表面処理法
JP135561/84 1984-06-29
JP135562/84 1984-06-29
JP59135561A JPS6115980A (ja) 1984-06-29 1984-06-29 銅の表面処理法
JP15807/85 1985-01-30
JP60015807A JPS61173932A (ja) 1985-01-30 1985-01-30 金属と樹脂層との積層体の製造法

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EP0170414A2 EP0170414A2 (de) 1986-02-05
EP0170414A3 EP0170414A3 (en) 1986-12-30
EP0170414B1 true EP0170414B1 (de) 1991-04-17

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EP (1) EP0170414B1 (de)
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KR890004583B1 (ko) 1989-11-16
EP0170414A2 (de) 1986-02-05
DE3582531D1 (de) 1991-05-23
US4643793A (en) 1987-02-17
KR860000411A (ko) 1986-01-28
EP0170414A3 (en) 1986-12-30

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